EP0890556A1 - Dünnschicht für optik, zusammensetzung zu deren herstellung und damit hergestelltes uv-absorbierendes und wärmereflektierendes glas - Google Patents

Dünnschicht für optik, zusammensetzung zu deren herstellung und damit hergestelltes uv-absorbierendes und wärmereflektierendes glas Download PDF

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Publication number
EP0890556A1
EP0890556A1 EP97950387A EP97950387A EP0890556A1 EP 0890556 A1 EP0890556 A1 EP 0890556A1 EP 97950387 A EP97950387 A EP 97950387A EP 97950387 A EP97950387 A EP 97950387A EP 0890556 A1 EP0890556 A1 EP 0890556A1
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Prior art keywords
refractive index
thin film
oxide
optical thin
mol percent
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EP97950387A
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French (fr)
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EP0890556B1 (de
EP0890556A4 (de
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K. Nippon Sheet Gl. Co. Ltd. NAKAMURA
Koichi Nippon Sheet Gl. Co. Ltd. MAEDA
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Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/256—Coating containing TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S501/00—Compositions: ceramic
    • Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
    • Y10S501/905—Ultraviolet transmitting or absorbing

Definitions

  • the present invention relates to an optical thin film, in particular a high refractive index film suitable for giving a transparent glass substrate ultraviolet ray absorbing and thermic ray reflecting features by covering the transparent glass substrate surface with the same, and a covering composition for forming the high refractive index film, and ultraviolet ray absorbing and thermic ray reflecting glass using the high refractive index film.
  • ultraviolet ray absorbing and thermic ray reflecting glass having a high refractive index layer and a low refractive index layer, which have a ultraviolet ray absorbing power, alternately laminated on the surface of glass, and ultraviolet ray absorbing and thermic ray reflecting glass which allows visible light beams to pass through and is able to selectively reflect the thermic rays have been developed.
  • Japanese laid-open patent publication No. 345488 of 1994 discloses thermic ray reflecting glass composed of two layers of high refractive index layer and low refractive index layer, which is covered with a thermic ray reflecting layer.
  • the low refractive index layer described therein has a refractive index which is the middle between the glass substrate and the high refractive index layer. It can not be said that the thermic ray reflecting performance is sufficient since the thermic ray reflecting glass has two layers and the low refractive index layer thereof has a middle refractive index.
  • Japanese laid-open patent publication No. 177204 of 1992 discloses a ultraviolet ray and infrared ray cut filter
  • Japanese laid-open patent publication No. 104544 of 1996 discloses thermic ray reflecting and ultraviolet ray absorbing glass and a method for producing the same.
  • High refractive index film used for thermic ray reflecting glass disclosed in these publications employs a ultraviolet ray absorbing film mainly composed of cerium oxide or cerium oxide and titanium oxide as described in a literature [Akio Makishima, et al., J. Am. Ceram. Soc., 69[6]C-127-C-129 (1986)].
  • a film is composed so as to have a combination ratio of cerium oxide and titanium oxide so that the ultraviolet ray absorbing power can be displayed.
  • Japanese laid-open patent publication No. 239244 of 1996 describes ultraviolet ray absorbing glass which is composed of three layers of high refractive index layer, low refractive index layer and high refractive index layer, each layer having an optical film thickness from 170nm to 400nm, wherein it is disclosed that one layer of the two high refractive index layers consisting of titanium oxide is caused to contain cerium oxide, preferably to have a ratio by weight of cerium oxide to titanium oxide, which is 0.1 to 5.0.
  • Japanese laid-open patent publication No. 281023 of 1995 describes a high refractive index film containing titanium oxide and bismuth oxide and an incandescent lamp bulb having infrared ray reflecting film using the same.
  • the present invention was developed in order to solve these conventional shortcomings and problems, and it is therefore an object of the invention to provide an optical thin film having a comparatively high refractive index in order to heighten the thermic ray reflection selecting performance and having a ultraviolet ray absorbing performance and ultraviolet ray absorbing and thermic ray reflecting glass using the same.
  • the invention relates to an optical thin film containing titanium oxide, cerium oxide and bismuth oxide.
  • An optical thin film having a comparatively high refractive index according to the invention contains titanium oxide, cerium oxide and bismuth oxide. Titanium oxide is effective to increase the refractive index of thin film and to give a ultraviolet ray absorbing performance to the optical thin film, cerium oxide is effective to give a ultraviolet ray absorbing performance to the abovementioned optical thin film. If the ratio of cerium oxide in the thin film is too small, no effect of absorbing ultraviolet rays can be recognized. To the contrary, if the ratio of cerium oxide is too large, the refractive index will be lowered.
  • the ratio CeO 2 /(TiO 2 +CeO 2 ) of CeO 2 to the total of TiO 2 and CeO 2 is 0.99 to 80% in term of mol ratio where the oxidation state thereof is assumed to be TiO 2 and CeO 2 , more preferably, the ratio is 20 to 60%, and still further preferably the ratio is 30 to 50%.
  • the ratio of titanium oxide and bismuth oxide in the thin film it is necessary that the ratio, Bi 2 O 3 /(TiO 2 +Bi 2 O 3 ), of Bi 2 O 3 to the total of TiO 2 and Bi 2 O 3 is 1 to 96% in term of mol ratio of TiO 2 and Bi 2 O 3 where the oxidation state of bismuth is assumed to be Bi 2 O 3 , more preferably the ratio is 4 to 60%, and still further preferably the ratio is 4 to 50%.
  • the ratio of content of titanium oxide, cerium oxide, bismuth oxide in an optical thin film having a comparatively high refractive index and ultraviolet ray absorption according to the invention is a ratio within the area expressed by four-cornered shape ABCD consisting of A (4,1,95), B (98,1,1), C (20,79,1), and D (3,14,83) where in the three element composition of TiO 2 -CeO 2 -Bi 2 O 3 , the mol ratio of each of TiO 2 , CeO 2 , and Bi 2 O 3 is expressed by coordinate points (TiO 2 mol percent, CeO 2 mol percent, and Bi 2 O 3 mol percent) as shown in a graph of FIG.1, more preferably a ratio within the area of four-cornered shape EFGH consisting of E (36,9,55), F (77,20,3), G (39,59,2), and H (24,38,38), and still further preferably a ratio within the area of four-cornered shape IJK
  • the refractive index of thin film of titanium oxide and cerium oxide having ultraviolet ray absorbing performance depends on the heating temperature for forming a thin film, it is possible to increase the refractive index in a range from 0.01 to 1.00 by causing the thin film to contain bismuth oxide in a case of a thin film obtained by the same burning conditions.
  • an optical thin film which is a thin film obtained by the same burning conditions, consisting of TiO 2 , 60 percent by mol and CeO 2 , 40 percent by mol, and having ultraviolet ray absorbing performance, has, for example, a refractive index of 1.99 with respect to wavelength of 550nm, it is possible to obtain an optical thin film having ultraviolet ray absorbing performance and a high refractive index from 2.00 to 2.35 (wavelength 550nm) according to the invention which contains bismuth oxide. And an optical thin film according to the invention usually has a geometrical thickness from 50 to 500nm.
  • An optical thin film according to the invention contains titanium oxide,cerium oxide, and bismuth oxide.
  • the optical thin film may contain a bit of constituents for example, zirconium oxide, tantalum oxide, niobium oxide, tungsten oxide, antimony oxide, silicon oxide, etc., other than the abovementioned constituents, for example, 10 or less percent by mol in the total thereof.
  • ultraviolet ray absorbing and thermic ray reflecting glass can be obtained by making at least one layer of the abovementioned high refractive index layers an optical thin film having the abovementioned ultraviolet absorbing performance and high refractive index. It is preferable that at least two layers of the abovementioned three layers are of high refractive index layer.
  • the ultraviolet ray absorbing performance and thermic ray reflecting performance can be further improved by making all of the abovementioned high refractive index layers an optical thin film having the abovementioned ultraviolet ray absorbing performance and high refractive index.
  • the number of layers of the abovementioned high refractive index film and low refractive index film the more is the better since the refractive index of the set wavelength can be increased if the number of layers is large.
  • the number of layers is 7 or less, more preferably 5 or less, or still further, three layers are the most preferable.
  • a high refractive index layer may be firstly laminated on a transparent substrate, and a low refractive index film may be laminated thereon, and they may be laminated in the reversed order thereof.
  • the number of times of lamination is odd, wherein the uppermost layer or the lowermost layer is a high refractive index film layer.
  • the optical thin film thickness of a low refractive index film at the lowermost layer or the uppermost layer may be one-eighth of the set wavelength to cause the tone of color to be stabilized.
  • the abovementioned high refractive index film has a wavelength of one-fourth of light (thermic rays) having a wavelength from 680nm to 2000nm, that is, an optical film thickness from 170nm to 500nm, and further preferable that the film has a one-fourth wavelength of light having a wavelength from 700nm to 1200nm, that is, an optical thin film from 175nm to 300nm, whereby it is possible to increase the reflection index of a thermic ray area without greatly reducing the transmittance of visible light beams from the transmittance of transparent substrate itself.
  • the abovementioned low refractive index film may be acceptable if the refractive index thereof is smaller than that of the abovementioned high refractive index film.
  • the refractive index of the low refractive index film is equivalent to or smaller than the refractive index of a transparent substrate.
  • Float glass used as a transparent substrate usually has a refractive index of about 1.5.
  • a substance having, for example, a refractive index of 1.5 or less for example a film exclusively or mainly composed of silica, which has a refractive index of 1.46 (with respect to light having a wavelength from 460nm to 850nm), may be preferably used as a low refractive index film, and it is preferable that the substance has a 1/4 wavelength of thermic rays, that is, an optical thin film from 170nm to 500nm as well as an optical thin film of high refractive index film, and further preferable that the substance has a 1/4 wavelength of a wavelength from 700nm to 1200nm, that is, an optical thin film from 175nm to 300nm.
  • a spatter method, CVD method may be employed to form a high refractive index film and a low refractive index film according to the invention.
  • a sol-gel method is further preferable in view of the cost.
  • a spin coating method, dip coating method, flow coating method, roll coating method, gravure coating method, flexoprinting method, screen printing method, etc. may be used with respect to the coating by a sol-gel method.
  • a coating liquid composition by the sol-gel method used to form a high refractive index film according to the invention consists of a titanium compound, a cerium compound, a bismuth compound and a solvent and is obtained by blending a titanium compound, a cerium compound, a bismuth compound with an organic solvent.
  • Titanium alkoxide, titanium alkoxide chloride, titanium chelate, etc. may be used as a titanium compound.
  • Titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium n-buthoxide, titanium isobuthoxide, titanium methoxypropoxide, titanium steariloxide, titanium 2-ethylhexyoxide, etc. may be listed as titanium alkoxide.
  • Titanium chloridetriisopropoxide, titanium dichloridediethoxide, etc. may be listed as titanium alkoxide chloride. Titanium triisopropoxide (2,4-pentanedionate), titanium diisopropoxide (bis-2,4-pentanedionate), titanium aryl acetate triisopropoxide, titanium bis (triethanol amine) diisopropoxide, titanium di-n-buthoxide (bis-2, 4-pentanedionate), etc. may be listed as titanium chelate. Cerium nitrate 6 hydrate, cerium chloride, cerium isopropoxide, cerium t-buthoxide, cerium methoxy ethoxide, etc.
  • Bismuth nitrate, bismuth acetate, bismuth oxyacetate, bismuth chloride, bismuth hexafluoropentanedionate, bismuth t-pentoxide, bismuth tetramethyl heptanedionate, etc. may be listed as a bismuth compound.
  • titanium compound, cerium compound and bismuth compound are respectively calculated as if they are converted to TiO 2 , CeO 2 and Bi 2 O 3 , and they are expressed by coordinate points (TiO 2 , percent by mol, CeO 2 , percent by mol, and Bi 2 O 3 , percent by mol) of mol ratio where they are calculated as if they are converted to their oxides
  • the titanium compound, cerium compound, bismuth compound are contained in the abovementioned composition of coating liquid so that their mol ratio becomes a ratio which enters an area of four-cornered shape ABCD consisting of A (4,1,95), B (98,1,1), C (20,79,1), and D (3,14,83), more preferably an area of four-cornered shape EFGH consisting of E (36,9,55), F (77, 20,3), G (39, 59, 2) and H (24, 38, 38), and further preferably an area of four-cornered shape IJKL consisting of I (54,23,23
  • a coating liquid composition by a sol-gel method used to form a comparatively low refractive index film according to the invention consists of a silicate compound and a solvent.
  • this composition such which silicon alkoxide is blended with a solvent such as alcohol and is hydrolyzed and polymerized by an acid or basic catalyst may be used.
  • silicon alkoxide silicon methoxide, silicon ethoxide, or their oligomer may be used.
  • Hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, trichloro acetic acid, trifluoro acetic acid, phosphoric acid, fluoric acid, formate acid, etc. may be used as an acid catalyst.
  • Metal oxide other than silicon for example, titanium oxide, cerium oxide, bismuth oxide, aluminum oxide, zirconium oxide, etc. may be blended to silica to such a degree that the refractive index is not remarkably increased, in order to improve the mechanical strength of film, to improve the environment resisting property, or to adjust the refractive index.
  • Super fine particles of silica, and such which fluorine is contained in silica or silica is made porous to further lower the refractive index may be employed.
  • an organic solvent used in the coating liquid composition used to form the abovementioned high refractive index film and low refractive index film depends on a coating method, methanol, ethanol, isopropanol, buthanol, hexanol, octanol, 2-methoxyethanol, 2-ethoxyethanol, 2-buthoxyethanol, cellosolve acetate, diethyleneglycol monoethylether, hexyleneglycol, diethyleneglycol, tripropyreneglycol, diacetone alcohol, etc. may be listed as an organic solvent.
  • a coating liquid composition according to the invention may use the abovementioned solvents independently or in a plurality to adjust the viscosity, surface tension, etc.
  • the amount of use of solvent depends on a film thickness of a high refractive index film and lower refractive index film which are finally obtained, and a coating method to be employed, the amount of use of the solid content thereof is usually in a range from 1 to 20%.
  • the abovementioned coating liquid composition is coated onto a glass substrate by utilizing various kinds of the abovementioned coating methods. Thereafter, the coating liquid composition is dried for 5 to 120 minutes at a temperature from 100 to 300 °C in an acid atmosphere (in the air), and is burned for 1 to 100 minutes at a temperature from 500 to 800 C, thereby forming a high refractive index film or a low refractive index film.
  • drying and burning are carried out independently for each of high refractive index film and low refractive index film to be laminated, the burning may be collectively carried out after the high refractive index film and low refractive index film are coated and dried.
  • the drying instead of the abovementioned heat drying at 100 to 300 C, the drying may be carried out by irradiating ultraviolet rays or visible light beams for 10 seconds to 10 minutes, or both of them may be concurrently used.
  • an optical thin film according to the invention has a ultraviolet ray absorbing performance is bondage of Ti-O-Ce.
  • the refractive index is increased in a case where bismuth exists, it is considered that titanium and bismuth exist in a thin film in an independent or blended state of complex oxide Ti x Bi y O z of titanium and bismuth, for example, bismuth titanate analog, titanium oxide Ti x O z and bismuth oxide Bi y O z , or in a blended state with a crystal body or amorphous body, and it can be presumed that any one of these contributes to improvement of the refractive index.
  • ultraviolet ray absorbing and thermic ray reflecting glass having a visible light beam transmittance (Ya) more than 70%, a sunlight transmission (Tg) 60% or less, which is lower 15% than the visible light beam transmittance, and a ultraviolet ray transmittance less than 25% (according to ISO 9050, hereinafter, expressed in term of TUV (ISO)), without remarkably lowering the visible light beam transmittance of substrate glass and greatly changing the transmitting color and reflection color tone of the substrate glass.
  • Ya visible light beam transmittance
  • Tg sunlight transmission
  • ISO ultraviolet ray transmittance less than 25%
  • Nitric bismuth 5 hydrate (Bi material) of 24.9g was blended with 2-ethoxyethanol of 118.2g, tetraisopropoxy titanium (Ti material) of 170.7g was added thereto, wherein they were agitated at 60 °C for three hours. After they were cooled to a room temperature, a liquid obtained by dissolving nitric cerium 6 hydrate (Ce material) of 173.4g in 2-ethoxyethanol of 120g was added thereto and they were agitated at a room temperature for one hour.
  • a solution composition for forming a high refractive index film which corresponds to "A" solution of A1 in Table 1.
  • composition ratio (mol ratio) in Table 1 by adjusting the amount of addition thereof, thereby causing 13 kinds of compositions, from A2 to A14, containing TiO 2 -CeO 2 -Bi 2 O 3 to be adjusted.
  • composition "A” solution was coated by a spin coating method onto a soda lime glass plate (thickness: 3.5mm, visible light beam transmittance: 90%, sunlight beam transmittance: 84.7%, ultraviolet ray transmittance (wavelength 370nm): 76.2%, refractive index: about 1.54 and 1.50 with respect to wavelengths 460nm and 850nm, respectively) ultrasonically treated in alkali water solution for five minutes and subsequently in pure water for five minutes. After the glass plate was dried at 250 °C for 1.5 hours, the plate was heated and burned in an electric hearth heated to 720 °C for two minutes.
  • the films thus obtained is about 100nm thick, and the refractive index (measurement wavelength, 370nm, 550nm, and 900nm) and attenuation coefficient of the film itself (measurement wavelength: 370nm) are shown in Table 1. Furthermore, the refractive index was measured by ellipsometry. The results of having observed the appearance of film by eyes are shown in Table 1, wherein a film having nothing abnormal was marked as "GOOD” and film having a crack was marked as "CRACK".
  • the film has a refractive index of 2.20 or more for the measurement wavelength of 370nm, 2.00 or more for the measurement wavelength of 550nm, 1.96 or more for the measurement wavelength of 900nm, and attenuation coefficient is 0.15 or more for 370nm.
  • compositions of optical films of the respect embodiments and comparison examples are plotted in a three-element composition graph on the basis of TiO 2 -CeO 2 -Bi 2 O 3 in FIG.1.
  • Ethylsilicate (Colcoat, Ltd., [Ethyl silicate 40]) 150g was blended with ethylcellosolve 132g, and hydrochloric acid of 0.1 mol/L, 18g, was added thereto. Thereafter, they were agitated at a room temperature for two hours. (“B" solution).
  • the glass plate was dried at 250 °C for 1.5 hours, the same was heated and burned in an electric hearth heated to 500 °C for sixty minutes to make the second layer composed of silica. Furthermore, "A" solution which is the same as the abovementioned A4 was coated on the second layer, and the glass plate was dried and burned by the method described in embodiment 1 to make the third layer. Furthermore, the thickness of each layer was determined by a simulation calculation within a range where the transmitting color tone and reflecting color tone of the film-attached glass plate becomes nearly the same as those of the substrate, so that the sunlight transmittance is minimized. Still furthermore, the thickness of the respective layers in embodiments 14 to 16 and comparison examples 3, 4 were determined as well.
  • the geometrical thickness of the first layer was 98nm, that of the second layer was 151nm, and that of the third layer was 90nm, wherein the visible light beam transmittance was 79.4%, the sunlight transmittance was 58.6%, the transmittance for 370nm was 21.0%, and TUV (ISO) was 19.4%.
  • the color tone the transmitting color tone and reflecting color tone of the glass surface were the same as those of the substrate.
  • the optical film thickness of the first, second and third layers was respectively 214.6nm, 220.5nm, and 197.1nm when being calculated by using the values of the refractive index (2.19, 1.46 and 2.19) with respect to light of wavelength of 900nm.
  • Embodiment 14 was prepared as in embodiment 13, except that a green soda lime glass plate (3.5mm thick, visible light beam transmittance: 81.0%, sunlight transmittance: 60.8%, ultraviolet ray transmittance (370nm): 52.6%, ultraviolet ray transmittance (TUV (ISO)): 31.4%) was used as a substrate.
  • the geometrical thickness of the first layer was 109nm, that of the second layer was 142nm, and that of the third layer was 91.5nm, wherein the visible light beam transmittance was 72.1%, the sunlight transmittance was 43.8%, the transmittance for 370nm was 14.6%, and TUV (ISO) was 8.7%.
  • the color tone both the transmitting color tone and reflecting color tone of the glass surface were the same as those of the substrate.
  • Embodiment 15 was prepared as in embodiment 13, except that a bronze-colored soda lime glass plate (3.5mm thick, visible light beam transmittance: 79.3%, sunlight transmittance: 72.68%, ultraviolet ray transmittance (370nm): 57.7%, ultraviolet ray transmittance (TUV (ISO)): 38.2%) was used as substrate.
  • the geometrical thickness of the first layer was 98nm
  • that of the second layer was 148nm
  • that of the third layer was 95nm
  • the visible light beam transmittance was 72.2%
  • the sunlight transmittance was 52.1%
  • the transmittance for 370nm was 16.6%
  • TUV (ISO) was 9.8%.
  • the color tone both the transmitting color tone and reflecting color tone of the glass surface were the same as those of the substrate.
  • Embodiment 16 was prepared as in embodiment 13, except that a green glass (3.5mm thick, visible light beam transmittance: 72.8%, sunlight transmittance: 48.8%, ultraviolet ray transmittance (370nm): 26.9%, ultraviolet ray transmittance (TUV (ISO)): 9.5%) having ultraviolet ray absorbing power was used as a substrate.
  • a green glass 3.5mm thick, visible light beam transmittance: 72.8%, sunlight transmittance: 48.8%, ultraviolet ray transmittance (370nm): 26.9%, ultraviolet ray transmittance (TUV (ISO)): 9.5%) having ultraviolet ray absorbing power was used as a substrate.
  • TUV (ISO) was 3.4%
  • the visible light beam transmittance was 72.2%
  • the sunlight transmittance 37.6%. and the color tones in transmittance and reflection was the same as those of the substrate.
  • Embodiment 17 was prepared as in embodiment 13, except that a bronze-colored glass (3.5mm thick, visible light beam transmittance: 73.9%, sunlight transmittance: 65.3%, ultraviolet ray transmittance (370nm): 29.7%, ultraviolet ray transmittance (TUV (ISO)): 9.6%) having ultraviolet ray absorbing power was used as a substrate.
  • the transmittance for 370nm was 7.4%
  • TUV (ISO) was 3.7%
  • the visible light beam transmittance was 72.0%
  • the sunlight transmittance 49.4%. and the color tones in transmittance and reflection was the same as those of the substrate.
  • each kind of glass substrates with a coated film consisting of three layers, it is possible to obtain ultraviolet ray absorbing and thermic ray reflecting glass having a high thermic reflecting performance, especially film-attached glass having a sunlight transmittance of 60% or less and value (visible light beam transmittance - sunlight transmittance) of 15% or more, and a ultraviolet ray transmittance (TUV(ISO)) of 25% or less with the visible light beam transmittance maintained at a high value, especially 70% or more.
  • a sunlight transmittance 60% or less and value (visible light beam transmittance - sunlight transmittance) of 15% or more
  • a ultraviolet ray transmittance (TUV(ISO)) of 25% or less with the visible light beam transmittance maintained at a high value, especially 70% or more.
  • the values of the visible light beam transmittance, sunlight transmittance and ultraviolet ray transmittance (TUV(ISO)) of a glass substrate are respectively defined to be Ya1, Tg1, Tuv1
  • the values of the visible light beam transmittance, sunlight transmittance and ultraviolet ray transmittance (TUV(ISO)) of the abovementioned film-attached glass plate are respectively defined to be Ya2, Tg2 and Tuv2
  • the visible light beam transmittance, sunlight transmittance and ultraviolet ray transmittance of the three-layered film itself are respectively defined to be (Ya2/Ya1), (Tg2/Tg1) and (Tuv2/Tuv1), in embodiments 13 to 17, a three-layered film can be obtained, which has a performance of (Ya2/Ya1) 90% or more, (Tg2/Tg1) 82% or less and (Tuv2/Tuv1) 40% or less.
  • Comparison example 3 was prepared as in embodiment 13, except that "A" solution of A13 which was used in comparison example 1 was used instead of "A” solution of A4 used in embodiment 13.
  • the geometrical thickness of the first layer was 123nm
  • that of the second layer was 159nm
  • that of the third layer was 109nm
  • the ultraviolet ray transmittance was 28.6% for a wavelength of 370nm of the film-attached glass obtained
  • TUV(ISO) was 25.5%
  • the visible light beam transmittance was 75.0%.
  • the sunlight transmittance was 66.7%, and the value of (Tg2/Tg1) was 91.9%, wherein the thermic ray shielding power was inferior to embodiment 13 in which [the sunlight transmittance was 58.6% and the value of (Tg2/Tg1) was 80.7%].
  • the color tones in transmission and reflection were almost the same as those of the substrate.
  • Comparison example 4 was prepared as in embodiment 13, except that "A" solution of A14 which was used in comparison example 2 was used instead of "A” solution of A4 used in embodiment 13.
  • the visible light beam transmittance of the film-attached glass thus obtained was 78.4% and the sunlight transmittance thereof was 60.1%. Furthermore, the transmittance for 370nm was 54.3%, TUV(ISO) was 50.6%, and the value of (Tuv2/Tuv1) was 94.8%.
  • Comparison example 4 was remarkably inferior in the ultraviolet ray absorbing performance to embodiment 13 in which [TUV(ISO) was 19.4% and the value of (Tuv2/Tuv1) was 36.3%]. The color tones in transmission and reflection were almost the same as those of the substrate.
  • glass according to the invention is suitable for optical materials such as ultraviolet ray absorbing and thermic ray reflecting glass.
EP97950387A 1996-12-25 1997-12-25 Dünnschicht für optik, zusammensetzung zu deren herstellung und damit hergestelltes uv-absorbierendes und wärmereflektierendes glas Expired - Lifetime EP0890556B1 (de)

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Application Number Priority Date Filing Date Title
JP34479996 1996-12-25
JP344799/96 1996-12-25
JP34479996 1996-12-25
PCT/JP1997/004812 WO1998029352A1 (fr) 1996-12-25 1997-12-25 Mince film a usage optique, composition pour la formation de ce film, et verre absorbant les ultraviolets et thermoreflechissant constitue par un tel film

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EP0890556A1 true EP0890556A1 (de) 1999-01-13
EP0890556A4 EP0890556A4 (de) 1999-04-14
EP0890556B1 EP0890556B1 (de) 2002-04-24

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EP (1) EP0890556B1 (de)
DE (1) DE69712194T2 (de)
WO (1) WO1998029352A1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000027771A1 (en) * 1998-11-09 2000-05-18 Ppg Industries Ohio, Inc. Solar control coatings and coated articles
WO2003099735A3 (de) * 2002-05-27 2004-12-09 Inst Neue Mat Gemein Gmbh Substrat mit einer titanoxid/ceroxid-schutzschicht
US7352118B2 (en) 2003-12-10 2008-04-01 General Electric Company Optimized ultraviolet reflecting multi-layer coating for energy efficient lamps
CN103395310A (zh) * 2013-07-04 2013-11-20 广东星星光电科技有限公司 一种具有3d效果的手机玻璃的复合印刷工艺
CN103693862A (zh) * 2013-12-19 2014-04-02 海南中航特玻材料有限公司 具有防紫外线和红外线双重功能的在线镀膜玻璃及制备方法
CN108290780A (zh) * 2015-10-22 2018-07-17 康宁股份有限公司 抗紫外光的制品及其制造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6620493B2 (en) * 2000-03-07 2003-09-16 Fukuvi Chemcial Industry Co Ltd Reflection-reducing film
US20040259713A1 (en) * 2003-06-11 2004-12-23 3M Innovative Properties Company Microspheres comprising titania and bismuth oxide
US7513941B2 (en) 2005-11-14 2009-04-07 3M Innovative Properties Company Pavement marking, reflective elements, and methods of making micospheres
KR101202345B1 (ko) * 2006-02-06 2012-11-16 삼성디스플레이 주식회사 고전도성 습식 코팅 조성물 및 이로부터 제조된 고전도성박막
CN102574730A (zh) 2009-08-21 2012-07-11 3M创新有限公司 路面标记、反射元件以及制备微球的方法
US8850836B2 (en) * 2010-10-11 2014-10-07 Shaam P. Sundhar Temperature control system
US20140186613A1 (en) * 2012-12-27 2014-07-03 Guardian Industries Corp. Anti-reflection coatings with self-cleaning properties, substrates including such coatings, and related methods
CN103074978B (zh) * 2013-02-18 2016-04-27 上海理工大学 一种带有紫色装饰薄膜的装饰板材及其制备方法
RU2542997C1 (ru) * 2014-02-25 2015-02-27 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" Просветляющее тонкопленочное покрытие на основе оксидных соединений кремния(iv) и висмута(iii)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1496542A1 (de) * 1964-09-05 1970-02-05 Jenaer Glaswerk Schott & Gen Glasgegenstand mit UV-absorbierendem Schutzbelag und Verfahren zu seiner Herstellung
FR2391173A1 (fr) * 1977-05-17 1978-12-15 Saint Gobain Verre reflechissant les rayons calorifiques
JPH07291665A (ja) * 1994-04-25 1995-11-07 Asahi Glass Co Ltd 金属酸化物被膜形成用塗布液と該塗布液による被膜の製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD158176A3 (de) * 1980-09-25 1983-01-05 Herbert Buerger Hochbrechendes optisches glas mit verbesserter transmission
DE3404363A1 (de) * 1984-02-08 1985-08-14 Schott Glaswerke, 6500 Mainz Hoch pbo-haltige glaeser im system sio(pfeil abwaerts)2(pfeil abwaerts)pbo-m(pfeil abwaerts)2(pfeil abwaerts)o mit erhoehter chemischer bestaendigkeit
JPH05215915A (ja) * 1992-01-31 1993-08-27 Asahi Optical Co Ltd 多層反射増加膜
JPH07281023A (ja) * 1994-04-05 1995-10-27 Mitsubishi Materials Corp 高屈折率膜、その形成用組成物及びその形成方法並びに白熱電球
JPH08239244A (ja) * 1995-03-03 1996-09-17 Asahi Glass Co Ltd 紫外線吸収ガラス
US5976678A (en) * 1996-02-27 1999-11-02 Nippon Sheet Glass Co., Ltd. Colored film-covered glass articles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1496542A1 (de) * 1964-09-05 1970-02-05 Jenaer Glaswerk Schott & Gen Glasgegenstand mit UV-absorbierendem Schutzbelag und Verfahren zu seiner Herstellung
FR2391173A1 (fr) * 1977-05-17 1978-12-15 Saint Gobain Verre reflechissant les rayons calorifiques
JPH07291665A (ja) * 1994-04-25 1995-11-07 Asahi Glass Co Ltd 金属酸化物被膜形成用塗布液と該塗布液による被膜の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 096, no. 003, 29 March 1996 & JP 07 291665 A (ASAHI GLASS CO LTD), 7 November 1995 *
See also references of WO9829352A1 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000027771A1 (en) * 1998-11-09 2000-05-18 Ppg Industries Ohio, Inc. Solar control coatings and coated articles
WO2003099735A3 (de) * 2002-05-27 2004-12-09 Inst Neue Mat Gemein Gmbh Substrat mit einer titanoxid/ceroxid-schutzschicht
US7352118B2 (en) 2003-12-10 2008-04-01 General Electric Company Optimized ultraviolet reflecting multi-layer coating for energy efficient lamps
CN103395310A (zh) * 2013-07-04 2013-11-20 广东星星光电科技有限公司 一种具有3d效果的手机玻璃的复合印刷工艺
CN103395310B (zh) * 2013-07-04 2016-04-20 广东星弛光电科技有限公司 一种具有3d效果的手机玻璃的复合印刷工艺
CN103693862A (zh) * 2013-12-19 2014-04-02 海南中航特玻材料有限公司 具有防紫外线和红外线双重功能的在线镀膜玻璃及制备方法
CN103693862B (zh) * 2013-12-19 2016-03-30 海南中航特玻材料有限公司 具有防紫外线和红外线双重功能的在线镀膜玻璃及制备方法
CN108290780A (zh) * 2015-10-22 2018-07-17 康宁股份有限公司 抗紫外光的制品及其制造方法

Also Published As

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EP0890556B1 (de) 2002-04-24
DE69712194T2 (de) 2002-11-14
US6153127A (en) 2000-11-28
DE69712194D1 (de) 2002-05-29
WO1998029352A1 (fr) 1998-07-09
EP0890556A4 (de) 1999-04-14

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